Polypropylene containing a dye-receptive modifier which comprises polyal-kyleneimine or mixztures thereof with an epoxy resin



Get. 15, 1963 ,CAPPUCClO r 3,107,228

POLYPROPYLENE CONTAINING A DYE-RECEPTIVE MODIFIER wHIcH COMPRISES POLYALKYLENEIMINE 0R MIXTURES THEREOF- WITH AN EPOXY RESIN Filed D60. 12, 1957 o 5 7 15 so 60 INVENTORS VlTTOR/O CAPPUCC/O FRANCESCO WCANTI PAOLO MALTESE ATTORNEYS United States Patent POLYPROPYLENE CONTAINING A DYE-RECEP- TIVE MODIFIER WHICH COMPRISES POLYAL- KYLENEIMINE OR MIXTURES THEREOF WITH AN EPOXY RESIN Vittorio Cappuccio, Francesco Vacanti, and Paolo Maltese, Terni, Italy, assignors to Montecatini Societit Generale per llndustria Mineraria e Chimica, Milan,

Italy Filed Dec. 12, 1957, Ser. No. 702,430 Claims priority, application Italy Dec. 12, 1956 12 Claims. (Cl. 26045.5)

This invention relates to improved textile fibers comprising polymeric olefins. More particularly, it relates to textile fibers of at least prevailingly crystalline polymeric olefins having improved dyeing and other physical properties.

Recently G. Natta and his co-workers have disclosed new polymers of the alpha-olefins CH CHR where R is a hydrocarbon radical, which polymers are of two different steric structures termed, by G. Natta, isotactic and atactic respectively.

The isotactic polymers are normally solid, linear, regular head-to-tail polymers consisting essentially of macromolecules in which substantially all of the asymmetric tertiary main-chain carbon atoms of adjacent monomeric units have the same steric configuration and the main chain of the macromolecules, when fully extended in a plane, shows substantially all of the R groups on one side of the plane and all of the hydrogen atoms bound to the tertiary carbon atoms on the opposite side. Because of their orderly steric structure, the isotactic polymers are crystalline or crystallizable.

The atactic polymers are also normally solid, linear, regular head-to-tail polymers but have a diiferent steric structure, being made up essentially of macromolecules in which tertiary asymmetric carbon atoms of the main chain having the same steric configuration have substantially a random distribution. When the main chain of the macromolecules of the atactic polymers is fully extended in a plane, it shows the R groups and the hydrogen atoms bound to the tertiary carbon atoms substantially in random distribution on the two sides of the plane. Due to their disorderly steric structure, the atactic polymers are amorphous and non-crystallizable.

As Natta et al. have shown, the isotactic and atactic polymers are, in general, obtained in admixture when the alpha-olefin is polymerized with the aid of certain catalysts prepared from compounds of transition metals of groups IV to VI of the periodic table (according to Mendeleev) and organometallic compounds of groups II-III of the table. When the mixtures are obtained, the polymers can be separated on the basis of their different steric structures by means of selective solvents.

Natta et al. have shown, further, that by using specific selected catalysts of the general type described hereinabove, the polymerization of the alpha-olefin can be oriented to the production of polymerizates prevailingly consisting of isotactic polymers, or to the production of polymerizates prevailing consisting of atactic polymers.

The polymerizates which prevailingly consist (for at least 60%) of isotactic polymers, and especially propylene polymerizates prevailingly consisting of isotactic poly- 3,107,228 Patented Oct. 15, 1963 propylene, can be formed into shaped articles, including fibers, yarns, films, etc. having exceptional mechanical properties.

However, the articles comprising the prevailingly isotactic (crystalline) polymers do not have good receptivity for swelling agents, dyes, pigments, etc. Moreover, such articles have a very low moisture-absorbing capacity and since those polymers have high insulating power the articles comprising them tend to accumulate electrostatic charges on the surface thereof which complicates fabrication of the fibers and yarns on conventional textileprocessingapparatus. These characteristics of the polymers somewhat hamper their practical utilization, particularly in the textile fiber field, in spite of their other very desirable properties such as high mechanical strength, elasticity, low density, etc.

It has been proposed by associates of the present inventors to improve the absorption capacity of shaped articles comprising the at least prevailingly isotactic polymers by grafting onto the surface thereof polymeric chains containing active groups or elements which facilitate the absorption of wetting agents, dyes, etc.

Such processes accomplishthe objective, but generally require special precautions in carrying them out in practice to avoid reduction in the mechanical strength of the shaped articles treated.

It has been proposed to improve the dyeing and other characteristics of such polymeric materials as polyacrylonitrile and polyvinylchloride by mixing those polymers with other polymers or copolymers of various kinds.

Due to the special properties of the prevailingly isotactic poly (alpha-olefins) it did not appear that such methods would be satisfactory when applied to them.

However, as disclosed in the pending application Ser. No. 683,981, filed September 16, 1957, now US. Patent No. 3,013,998, it was found that an afiinity for dyes can be imparted to the highly isotactic polymers by mixing the same with fusible epoxy resins, which were found to be compatible with the isotactic polymers and which appeared to be specific for that purpose.

Surprisingly, we find that, provided critical requirements as set forth herein are met, certain other polymeric materials having good absorption capacity for dyes, wetting agents, etc. are compatible with the isotactic polymers and can be mixed therewith, prior to shaping the polymers from solution or a melt, to obtain a mass which yields homogeneous shaped articles having the improved dyeing and other properties.

The polymeric modifying substance for use with the isotactic polymers must have the following critical characteristcs:

(a) A molecular weight of at least 1,000;

(b) Solubility or emulsifiability in the molten prevailingly isotactic poly alpha-olefin);

(c) A 2nd order transition temperature lower than the melting point of the poly (alpha-olefin);

(d) Insolubility in water or the capacity to be insolubilized during a spinning operation;

(e) An affinity for one or more classes of dyes.

The polymeric materials which we have found to have the requisite characteristics for use as modifier for the polymeric olefins and including the prevailingly isotactic poly (alpha-olefins), and which we have used advantageously for that purpose, include polyalkyleneimines in 3 which the alkylene group contains from 2 to 20 carbon atoms, reaction products of the polyalkyleneimines with alcohols, acids, esters, amides, aldehydes, halogenated hydrocarbons, halogen hydric acids, carbon disulfide, acrylonitrile, etc., copolymers of ethyleneimine, e.g., copolymers thereof with isocyanates, casein, and alkylene oxides, polyaminotriazoles, polyester resins obtained by the polycondensation of dicarboxylic acids, and glycols, polyamides including polycondensates of diamines with dicarboxylic acids, polycondensates of cyclic amides such as e-caprolactam, polyurethanes, polyureas, and in general polymeric materials containing the characteristic group .NH-CO, and which satisfy the requirements set forth herein.

For instance, when prevailingly isotactic polypropylene is mixed with a small amount of a polyethyleneimine meeting the requirements listed above (and which has, inherently, a strong afiinity for the acid dyes), the mixture can be spun into fibers having good mechanical properties and good receptivity for the acid dyes. These fibers can be mixed with natural fibers or with artificial proteinaceous fibers which are normally inherently receptive to the acid dyes, such as wool, Merinova, lanital, Acrilan, Orlon and the like, to obtain blends which can be dyed uniformly with the acid dyes.

Tests carried out with mixtures of prevailingly isotactic polypropylene and nitrogenous polymeric modifiers of the classes indicated, have given results similar to those obtained with the mixtures of the polypropyelene and polyethyleneimine.

The prevailingly isotactic poly (alpha-olefins) are most diflicultly dyed with the acid dyestuffs and, therefore, the possibility of readily dyeing the mixtures of those polymers with polyethyleneimines, derivatives thereof, and copolymers derived from ethyleneimine, with the acid dyes, etc., represents a very important aspect of this invention. However, the invention is not limited to use of the acid dyes and by selection of the specific type of polymeric modifying material mixed with the crystalline polymer, other types of dyes can be used successfully.

Thus, the polymeric polyethyleneimines and ethylenimine copolymers increase the receptivity of the prevail ingly crystalline polymeric olefins for dispersed acetate dyes. Very good results with the dispersed acetate dyes or other dyes have also been obtained on mixtures of the prevailingly crystalline polymeric olefins with other polymeric modifiers as disclosed herein and containing the NCCO-group.

The proportion of the polymeric modifier mixed with the prevailingly crystalline polymeric olefin can be varied and determined empirically depending on the particular polymeric modifier selected. In general, an amount of the polymeric modifier between 0.1% and 20% is sulficient.

It is advantageous, in some instances, to use mixtures of varying amounts of two or more of the polymeric modifiers, for example mixtures of two or more polymeric materials selected from polyamides, epoxy resins and the polyalkyleneimines.

When epoxy resins are used in mixture with polyalkyleneimines, it is preferred to use an epoxy resin the terminal epoxy groups of which have been blocked off by reaction with organic reactants containing one or more reactive functional groups, in order to avoid the formation of cross-linked and therefore infusible compounds with the polyimines.

The presence of these polymeric modifiers in the mixture with the isotactic poly (alpha-olefin) in amounts sufficient to modify the dye and moisture absorption capacity thereof does not influence the later operations of shaping the mixture to obtain fibers and then stretching and stabilizing the fibers and yarns. These operations are carried out in the same way, and under the same conditions, as are used in connection with a melt or solution of the isotactic polymer per se.

The fibers produced from the mixtures of the invention have mechanical properties which are substantially the same as those obtained from the prevailing crystalline polymeric olefins per se but have the improved dyeability, a much higher moisture absorption capacity, greater resistance to the accumulation of electrostatic charges and, surprisingly, in many cases exhibit a remarkable increase in stability to ultra-violet and natural light.

The results of tests to determine the stability of the modified fibers obtained according to this invention, to U.V. and natural light in comparison with other fibers are shown in the accompanying drawing, in which FIGURE 1 shows the resistance of the present fibers to ultra-violet light, the percentage of the initial tenacity retained by the fiber after exposure to the ultra-violet light source being reported on the ordinates, and the time of exposure expressed in hours, being reported on the abscissae.

FIGURE 2 shows the resistance of these fibers to natural light, the percent of the initial tenacity retained by the fibers being reported on the ordinates as a function of the days of exposure to natural light reported on the abscissae.

In FIGURE 1, curve 1 relates to fibers of prevailingly isotactic polypropylene; curve 2 to fibers obtained from a mixture of the polypropylene and 10% on the total polymer Weight of mixed polyethyleneimine and epoxy resin; curve 3 relates to the fibers of the mixture but after a final treatment with formaldehyde; and curve 4 relates to fibers of nylon 6,6.

In FIGURE 2, curve 1 relates to prevailingly isotactic polypropylene fibers; curve 2 to fibers from a mixture of the polypropylene and 10%, on the total polymer weight, of mixed polyethyleneimine and epoxy resin; curve 3 represents the findings as to fibers of the mixture but which were after-treated with formaldehyde.

While the invention has been discussed in terms of textile fibers, the present mixtures are also useful for the preparation of other shaped articles such as films, tapes, and in general articles of any shape and size which it is desired to dye to colors which are fast to wear, solvents, washing, light, etc., and which are antistatic, resistant to light, and have good moisture-absorbing property.

The following examples are given to illustrate specific embodiments of the invention, it being understood that these examples are not intended as limiting.

Example 1 About parts by weight of polypropylene having an intrinsic viscosity of 1.13 and 10 parts of a polyamide obtained by heating e-aminocaproic acid to 210-220 C. (melting point 203 C., Fikentschers value determined in 0.5% m-cresol solution, K=74.4, 2nd order transition temperature 5 0-5 5 C.) are mixed together. The spinning is carried out by melting the mixture at 265 C. and extruding it through a spinneret with 18 holes having a diameter of 0.4 mm. The yarn is stretched with a ratio of 114.5.

The yarn has the following characteristics:

Tenacity 2.39 g./den.

Elongation 36.4%.

Shrinking at C. in water 10%.

Resistivity 766x10 ohm cm.

Dyeability Good with acid dyes and acetate dyes.

Color fastness Generally good.

Moisture regain (determined by exposure of the samples for 70 hours in rooms with 50, 80 and 100% of relative humidity) 0.56% at 50% relative humidity; 1.55% at 80% relative humidity; 7.25% at 100% relative humidity.

Example 2 90 parts by weight of polypropylene having an intrinsic viscosity of 1.29 are mixed with parts of a polyamide obtained from hexamethylenediamine and sebacic acid (melting point 209 C.; Fikentschers value, determined in a 0.5 m-cresol solution, K=53). Spinning is carried out by melting this mixture at 250 C. and extruding it through a spinneret with 18 holes having a diameter of 0.4 mm. .The yarn is stretched with a ratio of 114.5.

The yarn has the following characteristics:

Tenacity 4.28 g./den.

Elongation 36.8%.

Shrinking at 100 C. in water 5.93%.

Resistivity 11.3 X10 ohmXcm.

Dyeability Good with acid dyes and acetate dyes.

Color fastness Generally good.

Moisture regain 6.4% with 50% relative humidity; 11.9% with 80% relative humidity; 35.0% with 100% relative humidity.

Another spinning run was carried out using a mixture of 90 parts polypropylene having an intrinsic viscosity of 1.29 and 10 parts of a similar polyamide having a K-value of 26.6. The results both of spinning and dyeability of the fibers and films are almost identical with those of the preceding run.

Example 3 90 parts by weight of polypropylene having an intrinsic viscosity of 1.13 are mixed with 10 parts of a polyurethane obtained by condensation of butylene glycol with toluenediisocyanate, and having a 2nd order transition temperature of 1418 C.

Spinning is carried out by melting the mixture at 250 C. and extruding it through a spinneret with 18 holes having a diameter of 0.4 mm. The yarn is stretched with a ratio of 1:45. The stretched fibers appear dyeable With acid dyes and acetate dyes.

Example 4 90 parts by weight of polypropylene with an intrinsic viscosity of 1.13 are mixed with 10 parts of a polyurea obtained by condensation of hexamethylenediamine and toluene-diisocyanate (Fikentscher K value 22.6, determined in a 0.5% m-cresol solution) The spinning is carried out by melting this mixture at 250 C. and extruding it through a spinneret with 18 holes having a diameter of 0.4 mm. The yarn is stretched with a ratio of 124.5. The stretched fibers can be dyed with acid dyes and acetate dyes.

Example 5 A mixture of crystalline polypropylene having an intrinsic viscosity of 1.17 with a resin obtained by condensation of pentarnethylenediamine with malonic acid, having a melting point of 191 C., is prepared. Mixing is carried out in a Werner type mixer at room temperature adding 15 parts polyamide resin to 85 parts polypropylene. The mass is melted at 250 C. and extruded through a spinneret with 18 holes having a diameter of 0.2 mm. The yarn obtained, stretched with a ratio of 1:5, has the following characteristics: Tenacity g./den 5.7 Elongation percent 22 A 10 g. sample was immersed in a dye bath containing the blue Navy Vialon fast dye (4% by weight of the fibers and 1 cc./liter of a dispersing agent). Dyeing was continued for 1 hour at 100 C. and after minutes 1 g. per liter of ammonium sulfate was added. The fibers have been then washed at 60 C. in a bath containing 1 g. per liter of the dispersing agent.

The fibers are colored a deep blue with a good fastness to light, rubbing and washing.

6 Example 6 970 g. crystalline polypropylene having an intrinsic viscosity of 1.13 are mixed with 30 g. of a polyethyleneimine having a relatively low molecular weight but above 1000 and a melting point of 25-30" C., obtained by polymerization of ethyleneimine with hydrochloric acid at C. for 5 hours. The mixture is melted at 240 C. and extruded through a spinneret with 18 holes (diameter 0.4 mm); the yarn obtained, stretched with a ratio of 1:4.5 has the following characteristics:

Tenacity 4 g./den.

Elongation 30% Moisture regain 1.2% with 50% relative humidity;

3% with 80% relative humidity; 7% with 100% relative humidity.

Resistivity 3.6 10 ohm. cm.

The dyeability of these fibers is very good with acid dyes. Yarns obtained from blends of the same fibers with wool are dyed with the following dyes obtaining uniform colors:

Novamine 2GP Yellow Red Amidonaphthol A 2B Fast Light Green 2G Alizarine Grey ZBL Dyeing is carried out according to the usual methods, with 3% by weight of the dye referred to the blend, in the presence of acetic acid.

Example 7 100 g. of epoxy resin obtained by reaction of epichlorhydrine and 4,4'-dioxy-diphenyl-dimethyl-methane (molecular weight 900, determined by ebullioscopy) are treated in the molten state with monoethanolamine for 20 minutes.

100 g. low molecular weight polyethyleneimine are then added to the molten mass while stirring. The molten mass with a 2nd order transition temperature of 10l5 C. and melting point of 60-75 C. is cooled, broken and powdered in a ball mill.

200 g. of this product are added to 1800 g. crystalline polypropylene with an intrinsic viscosity of 1.07. The mass is homogenized in a mixer melted at 210 C. and extruded through an 18-hole spinneret (diameter 0.4 mm.). Th yarn stretched with a ratio of 1245 has the following characteristics:

Tenacity 4.28 -g./ den. Elongation 36.8%. Resistivity 0%. Moisture regain--- 7.88 10 ohmx cm.

6.4% with 50% relative humidity;

11.9% with 80% relative humidity;

Shrinking in water at 100 C 35% with 100% relative humidity.

The yarns are dyed satisfactorily with the following dyes:

Wool Red B Alizarine Blue SE Fast Light Yellow 2G Yellow Eastman ZRGLF Red Cibacet B Blue Acetoquinone RHO Example 8 A mixture of parts by weight of polyethylene having a molecular weight of 18,000 with 10 parts of a 1:2 mixture of polyethyleneimine and epoxy resin (similar to that used in Example 7) is prepared.

This mix is homogenized in a mill and then extruded in order to obtain a monofilament having a diameter of 300 microns. Spinning is carried out by melting the mass at 200 C. The tibers can be dyed very well with the following wool acid dyes:

Fast Light Yellow 26 Brilliant Acid Green 26 Alizarine Blue BV Example 9 100 g. epoxy resin obtained by reaction of epichlorohydnine and 4,4-dioxydiphenyldimethylmethane (molecular weight 1400) are treated in the molten state with monoethanolamine for 25 minutes. 100 g. low molecular weight polyethyleneimine are then added to the molten mass 'while stirring. The molten mass is then cooled, broken up and powdered in a ball mill. 200 g. of this product are added to 1800 g. crystalline polypropylene with an intrinsic viscosity of 1.19, the mass is melted at 220 C. and extruded through an 18-hole spinneret (diameter 0.4 mm.).

The yarn stretched with a ratio of 1:4.5 has the following characteristics:

Tenacity 3.23 g./ den. Elongation 25.7%

Resistivity 2.06 X 10 ohm cm.

Example Fibers similar to those of Example 7 are spun using polypropylene with an intrinsic viscosity of 0.8. A yarn with the following characteristics is obtained:

Tenacity g./den 2.8 Elongation "percent" 23.1 j g./den 25 Elastic modulus "m 202 Strain ratio den./g 0.12 Stiffness -g./den 12.1 Toughness g./den 0.42

The yarn obtained as described can be treated with formaldehyde in order to still further improve its characteristics, in particular its stability to heat and UV. light. This treatment is carried out by boiling the yarn for 10 minutes in a 5% formaldehyde aqueous solution.

Example 11 80 g. polyethyleneirn-ine are dissolved in 200 cc. ethyl alcohol and 20 g. stearyl chloride are added. The mixture is refluxed for 4 hours. The solvent is eliminated by distillation under vacuum. A waxy resin with a softening point of 2540 C. is separated which is then mixed with 900 g. polypropylene having an intrinsic viscosity of 0.96. This mixture after homogenization in a mill is spun at 210 C. through a spinneret with 18 holes (0.4 diameter).

The characteristics of the yarn, after stretching with a ratio of 1:4.5 are as follows:

Tenacity 2.05 g./den.

Elongation 22%.

Resistivity 1.66 10 ohmXcm.

Moisture regain 1.7% with 50% relative humidity; 5.3% with 80% relative humidity; 42.2% with 100% relative humidity.

8 The fiber has a very good dyeability with the following dyes:

Wool Red B Alizarine Blue SE Brilliant Acid Green 2G Example 12 To g. polyethyleneimine 20 g. chlorinated parafiinic wax are added and the mixture is heated to 120 C. for 2 hours. The yellowish resin obtained is mixed with 900 g. polypropylene having an intrinsic viscosity of 0.97. This mixture is then spun at 250 C. The filaments obtained are stretched with a ratio of 1:4.5. They have the following characteristics:

Tenacity 3.65 g./den.

Elongation 28%.

Resistivity 4.65 10 ohmxcrn.

Moisture regain 0.9% with 50% relative hu midity; 10.2% with 80% relative humidity; 13.3% with relative humidity.

They also have good dyeability with the following dyes:

Aliza-rine Blue ACF Wool Red B Fast Light Yellow 2G Example 13 40 g. ditoluenediisocyanate are added to 80 g. polyethyleneimine. This rnass is heated to 60 C. for 6 hours.

A Waxy resin with a softening point of 25-40 C. is obtained which is mixed with 900 g. polypropylene having an intrinsic viscosity of 0.97. The mixture is spun at 250 C. The yarns can be satisfactorily dyed with the following acid dyes:

Fast Light Yellow 2G Wool Red B Alizarine Blue ACE and they present the following characteristics:

Tenacity 3.2 g./den.

Elongation 30%.

Resistivity 1X10 ohmxcrn.

Moisture regain 0.69% with 5 0% relative humidity; 0.8% With 80% relative humidity; 3.9% with 100% relative humidity.

Fast Light Yellow 26 Wool Red B Alizarine Blue ACE and present the following characteristics:

Tenacity 2.62 g./den. Elongation 19%. Resistivity 2.13 10 ohm cm. Moisture regain 1.5% with 50% relative humidity; 3.1% with 80% relative humidity; 12.3% with 100% relative humidity.

Example 15 900 g. crystalline polypropylene having an intrinsic viscosity of 1.07 are mixed with 100 g. of a polyester resin, obtained by condensation of sebacic acid and propylene glycol, having a 2nd order transition temperature of between -50 C. and -45 C., a molecular weight of 3,300-4,000 (determined by the cryoscopic method in acetic acid) and a softening point of -10 C. The mixture is melted at 250 and extruded through an 18-hole spinneret (0.4 mm. diameter).

The yarn obtained after stretching has very good dyeability with the acetate dyes.

As will be apparent from the examples given, other crystalline polymers besides the prevailingly isotactic poly (alpha olefins) can be modified advantageously in accordance with the invention and particularly linear, highly crystalline polyethylene.

So long as the modifying polymer or copolymer has a molecular weight of at least 1000, the upper limit on the molecular weight is not critical, provided the polymer is compatible with the polymeric olefin in the amounts used and has the other characteristics which we have determined are required for successfully modifying the dyeing and absorption properties of the shaped articles of the crystalline polymeric olefins without any appreciable damage to the other inherent desirable properties of the articles such as the mechanical strength.

Since various changes and modifications may be made in details in practicing the invention, without departing from the spirit thereof, we intend to include in the scope of the appended claims all such changes and variations as may be apparent to those skilled in the art.

What is claimed is:

1. A readily dyeable composition adapted to be formed into shaped articles having increased receptivity for dyes, said composition consisting essentially of l) polypropylene made up prevailingly of isotactic macromolecules and (2) from 0.1% to 20% by weight on the total weight of the composition of a Water-insoluble, polymeric, dyereceptive modifier dispersible in the polypropylene when the latter is melted, having a molecular weight of at least 1,000 and a 2nd order transition temperature below the melting point of the polypropylene, and which is a mixture of a polyalkyleneimine in which the alkylene group contains from 2 to 20 carbon atoms, with the reaction product of (A) an epoxy resin obtained by reacting epich-lorohydrin and 4,4-dioxy-diphenyl-dimethyl-methane, and (B) monoethanol amine.

2. A readily dyeable composition according to claim 1, characterized in that the polymeric, dye-receptive modifier is a mixture of polyethyleneimine with the epoxy resin-monoethanolamine reaction product.

3. A readily dyeable composition adapted to be formed into shaped articles having increased receptivity for dyes, said composition consisting essentially of (1) polypropylene made up prevailingly of isotactic macromolecules, and (2) from 0.1% to 20% by weight on the total weight of the composition of a water-insoluble, polymeric, dyereceptive modifier dispersible in the polypropylene when the latter is melted, having a molecular weight of at least 1,000 and a 2nd order transition temperature below the -melting point of the polypropylene, and selected from the group consisting of polyalkylenei-mines in which the alkylene group contains from 2 to 20 carbon atoms, and mixtures of said polyalkyleneimines with the reaction product of (A) an epoxy resin obtained by reacting epichlorohyd-rin and 4,4-dioxy-diphenyl-dimethyl methane, and (B) monoethanolamine.

4. A readily dyeable composition according to claim 3, characterized in that the polymeric, dye-receptive modifier is polyethyleneimine.

5. A process for producing readily dyeable shaped articles of polypropylene made up prevailingly of isotactic macromolecules and having improved dye-receptivity, which process comprises mixing the polypropylene with from 0.1% to 20% by weight on the total weight of the mixture of a water-insoluble readily dye-receptive, polymeric modifier which is dispersible in the polypropylene when the latter is melted, has a molecular weight of at least 1,000 and a 2nd order transition temperature below the melting point of the polypropylene, and is a mixture of a polyalkylenei-mine in which the alkylene group contains from 2 to 20 carbon atoms, with the reaction product of (A) an epoxy resin obtained by reacting epichlorohydrin and 4,4-dioxy-diphenyl-dimethyl methane, and (B) monoethanolamine, and shaping the composition to obtain a readily dyeable shaped article.

6. The process according to claim 5, characterized in that the readily dyeable polymeric modifier is a mixture of polyethyleimine with the epoxy resin-monoethanolamine reaction product.

7. A process for producing readily dyeable shaped articles of polypropylene made up prevailingly of isotactic macromolecules and having improved dye-receptivity, which process comprises mixing the polypropylene with from 0.1% to 20% by weight on the total weight of the mixture of a water-insoluble, readily dye receptive polymeric modifier which is dispersible in the polypropylene when the latter is melted, has :a molecular weight of at least 1,000 and a 2nd order transition temperature below the melting point of the polypropylene, and is selected from the group consisting of po-lyalkyleneimines in which the alkylene group contains from 2 to 20 carbon atoms and mixtures of the polyalkyleneimine with the reaction product of (A) an epoxy resin obtained by reacting epichlorohydrin and 4,4-dioxy-diphenyl-dimethylmethane, and (B) monoethanolamine, and shaping the mixture to obtain a dyeable shaped article.

8. The process according to claim 7, characterized in that the readily dyeable, polymeric modifier is polyethyleneimine.

9. Dyeable manufactured shaped articles consisting essentially of a mixture of (l) polypropylene made up prevailingly of isotactic macromolecules and (2) from 0.1% to 20% by Weight on the total weight of the mixture of a water-insoluble dye receptive polymeric modifier dispersible in the polypropylene when the latter is in the melted condition, the modifier having a molecular weight of at least 1,000 and a 2nd order transition temperature below the melting point of the polypropylene, and being a mixture of a polyalkyleneimine in which the alkylene group contains from 2 to 20 carbon atoms with the reaction product of (A) an epoxy resin obtained by reacting epichlorohydrin and 4,4-dioxy-diphenyl-dimethyl-methane, and (B) monoethanolamine.

10. Dyeable manufactured shaped articles according to claim 9, and characterized in consisting essentially of a mixture of (1) polypropylene and (2) a dye-receptive polymeric modifier which is a mixture of polyethyleneimine with the epoxy resin-monoethanolamine reaction product.

11. Dyeable manufactured shaped articles consisting essentially of a mixture of (l) polypropylene made up prevailingly of isotactic macromolecules and (2) from 0.1% to 20% by weight on the total weight of the mixture of a dye-receptive water-insoluble polymeric modi fier which is dispersible in the polypropylene when the latter is in melted condition, has a molecular weight of at least 1,000 and :a 2nd order transition temperature below the melting point of the polypropylene, and is selected from the group consisting of polyall yleneimines in which the alkylene group contains from 2 to 20 carbon atoms, and mixtures of the polyalkyleneirnines with the reaction product of (A) an epoxy resin obtained by reacting of epichlorohydrin and 4,4-dioxy diphenyl-dimethyl methane, and (B) monoethanolamine.

l2. Dyeable manufactured shaped articles according to claim 11, characterized in consisting essentially of a mixture of the polypropylene with polyethyleneimine.

(References on following page) References Cited in the file of this patent UNITED STATES PATENTS Pratt June 7, 1949 Gray Nov. 21, 1950 Craig Dec. 7, 1954 Field et a1. Jan. 17, 1956 Mowry et a1. May 1, 1956 Natta et a1 Apr. 14, 1959 Thompson Aug. 23, 1960 FOREIGN PATENTS Great Britain Feb. 15, 1937 Great Britain Feb. 7, 1947 Great Britain Dec. 3, 1948 OTHER REFERENCES Raff et =al., Polyethylene, published 1956 by Interscience Publishers, Inc., New York, pages 80, 175, 407 and 408 relied on. 

1. A READILY DYEABLE COMPOSITION ADAPTED TO BE FORMED INTO SHAPED ARTICLES HAVING INCREASED RECEPTIVITY FOR DYES, SAID COMPOSITION CONSISTING ESSENTIALLY OF (1) POLYPROPYLENE MADE UP PREVAILINGLY OF ISOTACTIC MACROMOLECULES AND (2) FROM 0.1% TO 20% BY WEIGHT ON THE TOTAL WEIGHT OF THE COMPOSITION OF A WATER-INSOLUBLE, POLUMERIC, DYERECEPTIVE MODIFIER DISPERSIBLE IN THE POLYPROPYLENE WHEN THE LATTER IS MELTED, HAVING A MOLECULAR WEIGHT OF AT LEAST 1,000 AND A 2ND ORDER TRANSITION TEMPERATURE BELOW THE MELTING OINT OF THE POLYPROPYLENE, AND WHICH IS A MIXTURE OF A POLYALKYLENEIMINE IN WHICH THE ALKYLENE GROUP CONTAINS FROM 2 TO 20 CARBON ATOMS, WITH THE REACTION PRODUCT OF (A) AN EPOXY RESIN OBTAINED BY REACTING EPICHLOROHYDRIN AND 4,4''-DIOXY-DIPHENYL-DIMETHYL-METHANE, AND (B) MONOETHANOLAMINE. 